EP2079774B1 - Impression par jet d'encre - Google Patents

Impression par jet d'encre Download PDF

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Publication number
EP2079774B1
EP2079774B1 EP07824530.5A EP07824530A EP2079774B1 EP 2079774 B1 EP2079774 B1 EP 2079774B1 EP 07824530 A EP07824530 A EP 07824530A EP 2079774 B1 EP2079774 B1 EP 2079774B1
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Prior art keywords
composition
ether
composition according
curable
water
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German (de)
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EP2079774A1 (fr
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Natasha Jeremic
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Xennia Technology Ltd
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Xennia Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the invention relates to curable inkjet compositions, particularly those suitable for use in thermal inkjet printing.
  • Inkjet printing processes fall into two main types: continuous processes and drop-on-demand (DOD) processes.
  • Continuous processes use electrically conductive inks to produce a stream of drops electrically charged ink that are deflected by an electric field to an appropriate location on a substrate.
  • DOD processes individual drops of ink are expelled from the nozzle of a print head either by vibration of a piezoelectric actuator (in piezoelectric inkjet printing) or by heating the ink to form a bubble (in thermal inkjet printing, also known as bubblejet printing).
  • Thermal inkjet printing has advantages over piezoelectric printing, with printers and print heads being lower cost and with the printing process being able to achieve better resolution.
  • Inkjet inks need to satisfy a number of requirements, including the following:
  • inks suitable for use in thermal inkjet printing must also comprise a volatile solvent which vapourises in use to form bubbles of ink.
  • Water is often chosen as such a solvent as it has a low viscosity and carries no ignition risk.
  • UV-curable inks are known and provide a greatly superior printing result than for non-curable inks. These typically comprise one or more monomers etc. curable in response to appropriate conditions, typically ultraviolet (UV), infra red (IR), microwave or heat.
  • UV ultraviolet
  • IR infra red
  • Inkjet inks which are cationically curable are therefore typically free of water.
  • curable inks comprising water.
  • cationically- and free-radically-curable monomers and oligomers tend to have limited solubility in water, and may undergo undesirable phase separation unless care is taken.
  • WO 2006/056781 discloses curable inks for use in inkjet printing having a viscosity less than 100 mPas, which contain cycloaliphatic epoxy compounds, oxetane monomers, hydroxy-containing compounds and optionally an allyl/vinyl ether monomer, together with at least one cationic photoinitiator, among other ingredients.
  • the exemplified inks have viscosities in the range 91.7 to 19.0 mPas at 25 °C.
  • the compositions are water-free.
  • US 2005/0171237 discloses a cationically curable composition, suitable for use in piezoelectric inkjet printing, comprising a low viscosity reactive resin comprising an oxetane and a cyloaliphatic epoxy resin, in combination with a higher viscosity reactive resin of similar composition.
  • the compositions are substantially non-aqueous.
  • US 2005/0090580 discloses an ink for inkjet recording comprising oxetanes and aliphatic epoxy compounds, see paragraph 75).
  • the compositions are curable by a cationic mechanism. It is generally desired that the composition is prepared so as not to contain any volatile component such as water and organic solvents.
  • US 2004/0166253 concerns inkjet inks suitable for use in piezoelectric inkjet printing, where the viscosity of the ink is reduced and has good performance under high humidity conditions.
  • the composition comprises an alicyclic epoxy material, an oxetane and optionally a vinyl ether.
  • the composition does not contain water.
  • the invention provides a single phase curable composition having a viscosity of from 1 to 10 mPas at 25°C as measured according to the description for use in thermal inkjet printing, comprising at least one cationically curable material, at least one cationic photoinitiator and water, wherein the cationically curable material comprises an oxetane functional monomer, and wherein: either a) the cationically curable material comprises limonene monoxide or limonene dioxide, or b) the composition includes at least one free radically curable material and includes one or more curable N-vinyl monomer materials.
  • compositions provide some or all of the advantages of water-free compositions but with the additional advantages associated with water being present, such as low viscosity and allowing the compositions to be safely used in thermal inkjet printing.
  • compositions of the invention are used in conventional manner, e.g. using a thermal inkjet printer.
  • the compositions are printed onto the intended substrate and exposed to an appropriate curing regime depending on the nature of the curable materials, e.g. involving exposure to UV light, heat, etc.
  • a drying step may also be required, e.g. using exposure to microwaves.
  • compositions may be printed onto a variety of substrates, and find particular use with non-porous and semi-porous substrates such as metals, metallized films, glass, plastics (e.g. polyesters such as polyethylene terephthalate (PET), low density (LD) polyethylene, and orientated polystyrene, high density (HD) polyethylene, polypropylene, polyvinyl chloride (PVC), polycarbonate, polyimide film etc.
  • PET polyethylene terephthalate
  • LD low density
  • HD high density
  • PVC polyvinyl chloride
  • the invention can provide compositions that are fast drying and produce good quality prints of high durability.
  • the resulting prints may satisfy the requirements of good scratch resistance, wetfastness, flexibility and optical density (for coloured inks).
  • the compositions find particular application in industrial printing onto non-porous substrates.
  • the term "single phase” is used to mean that the curable materials are fully in solution, being dissolved in water and co-solvent or being fully miscible therewith. No phase separation or settlement occurs.
  • the single phase composition may nevertheless optionally carry other materials in solid form to achieve required application properties.
  • the ink compositions of the present invention can optionally comprise dye or pigment.
  • a dye is a colorant, which is dissolved in the carrier medium, while a pigment is a colorant that is insoluble in the carrier medium, but is dispersed or suspended in the form of small particles, often stabilized against flocculation and settling by the use of dispersing agents.
  • compositions according to the invention may contain a wide range of water levels, such as from 2 to 50 wt % of the composition. However, care must be taken that levels are not so low that overheating occurs when thermally printed or that levels are not so high that phase separation occurs. Water levels are preferably in the range of from 5 to 40 wt %, more preferably 10 to 30 wt % of the composition.
  • DOD inkjet inks must have low viscosities in order to perform to acceptable standards. This is particularly the case for thermally printed inks. Viscosities are preferably from 5 to 10 mPas.
  • curable refers to functionality directly or indirectly pendant from a surface-treated particle, monomer, oligomer, polymer, or other constituent (as the case may be) that participate in polymerization and/or crosslinking reactions upon exposure to a suitable source of curing energy.
  • Such functionality generally includes not only groups that cure via a cationic mechanism upon energy exposure but also groups that cure via a free-radical mechanism.
  • the energy source used for achieving polymerization and/or crosslinking of the curable materials may be actinic (e.g. radiation having a wavelength in the ultraviolet or visible region of the spectrum), accelerated particles (e.g., electron beam radiation), thermal (e.g. heat or infrared radiation), or the like.
  • the energy is actinic radiation, because such energy provides excellent control over the initiation and rate of polymerization and/or crosslinking.
  • actinic radiation can be used for curing at relatively low temperatures. This avoids degrading or evaporating components that might be sensitive to the relatively high temperatures that might be required to initiate polymerization and/or crosslinking of the energy curable groups when using thermal curing techniques.
  • Suitable sources of curing energy include lasers, electron beams, mercury lamps, xenon lamps, carbon arc lamps, tungsten filament lamps, sunlight, low intensity ultraviolet light (UV), and the like.
  • UV light for polymerization tends to form higher molecular weight polymers as compared to many other kinds of curing energy. Accordingly, when it is desired to form higher molecular weight materials upon curing, the use of UV light is preferred.
  • the cationically curable materials harden on curing following exposure to a suitable curing stimulus e.g. UV, heat, or infra red (with appropriate initiators being used) after printing to form printed material usually in the form of a film.
  • a suitable curing stimulus e.g. UV, heat, or infra red (with appropriate initiators being used) after printing to form printed material usually in the form of a film.
  • Preferred cationically curable materials are epoxy functional monomers containing one or more epoxy functionalities in the molecule.
  • Epoxy functional monomers which are cycloaliphatic epoxy functional monomers are particularly preferred.
  • Suitable cycloaliphatic epoxies include, but are not limited to 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (ERL-4421, Union Carbide Corp.), (Cyracure UVR-6105, UVR-6107, UVR-6110, Dow Chemicals), bis-(3,4-epoxycyclohexylmethyl) adipate (Cyracure UVR-6128, Dow Chemicals), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexene carboxylate (ERL-4201TM, Union Carbide Corp.), bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate (ERL-4289TM, Union Carbide Corp.), bis(2,3-epoxycyclopentyl) ether (ERL-0400TM, Union Carbide Corp.), aliphatic epoxy modified with polypropylene glycol
  • the epoxy functional monomers are suitably present in an amount in the range 1 to 60 % by weight, preferably 1 to 40 % by weight and more preferably 20 to 30 % by weight of the composition. However, when optional free radically curable materials are also present the epoxy functional monomers are suitably present in an amount in the range 0-10 % by weight, preferably 2-5 % by weight of the composition.
  • oxetane functional monomers containing one or more oxetane rings in the molecule.
  • Suitable oxetanes include, but are not limited to 3-ethyl-3-hydroxymethyl oxetane (OXT-101, Toa Gosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (OXT-121, Toa Gosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211, Toa Gosei Co., Ltd.), di(1-ethyl-3-oxetanyl)methylether (OXT-221, Toa Gosei Co.
  • 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT-212, Toa Gosei Co., Ltd.) and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT-212, Toa Gosei Co., Ltd.), and specifically preferably utilized are 3-ethyl-3-hydroxymethyl oxetane, and di(1-ethyl-3-oxetanyl)methyl ether. These oxetanes can be employed alone or in combinations thereof. (OXT-101, 121, 211, 221 and 212 are Trade Marks). 3-ethyl-3-hydroxymethyl oxetane (OXT-101) is particularly preferred because it has been found to be water tolerant.
  • the oxetanes are suitably present in an amount in the range 5-50 % by weight, preferably 7-40 % by weight of the composition. However, when free radically curable materials are also present -the oxetanes are suitably present in an amount in the range 1-20 % by weight, preferably 3-15 % by weight of the composition.
  • Allyl and/or vinyl ether monomers may be desirably included into the compositions of the present invention. Such materials provide numerous benefits e.g. being of low viscosity and cure rapidly by both free radical and cationic photoinitiators.
  • Suitable vinyl ether compounds include, but are not limited to vinyl- and divinyl ether compounds such as ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether (TEGDVE), propylene glycol divinyl ether, dipropylene glycol divinyl ether, 1,4-butanediol vinyl ether, 1,4-butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynon
  • vinyl ether compounds when taking into account viscosity, curability, adhesion properties, and surface hardness, mono-, divinyl or trivinyl ether compounds are preferred, and divinyl ether compounds are specifically preferred.
  • the vinyl ether compounds may be employed individually or in combinations thereof.
  • Vinyl ethers may be present in an amount in the range 0-40 % by weight, preferably 5-30 % by weight of the composition. However, when free radically curable materials are also present, the vinyl ethers are suitably present in an amount in the range 0-40 % by weight, preferably 2-5 % by weight of the composition.
  • compositions comprising cationically curable materials, they may also comprise free radically curable materials, including one or more N-vinyl monomer materials, and free radical photoinitiators. Such materials are sometimes known in the art as "hybrid" compositions.
  • Free-radically curable materials useful in the hybrid inkjet ink compositions of the present invention preferably include one or more monofunctional acrylates.
  • Suitable commercially available free-radically curable materials include the following available from Sartomer: tridecyl acrylate (SR 489TM), isodecyl acrylate (SR 395), 2-phenoxy acrylate (PEA) (SR 339CTM), lauryl acrylate (SR 335TM), 2-(2-ethoxy-ethoxy)ethyl acrylate (EOEOEA) (SR 256TM), tetrahydrofurfuryl acrylate (THFA) (SR 285TM), and isobornyl acrylate (IBOA) (SR 506DTM).
  • Monofunctional acrylates have good solvency, low viscosity, high flexibility and good adhesion to plastic and to difficult substrates.
  • a monofunctional acrylate suitably present in an amount in the range 1-15 %, preferably in the range 5-8 % by weight of the composition.
  • the free-radically curable materials in the hybrid inkjet ink compositions of the present invention preferably include one or more polyalkene glycol acrylates. Good results have been obtained using alkoxylated trimethylolpropane acrylates, suitably present in an amount in the range 1-15 %, preferably in the range 5-8 % by weight of the composition.
  • Oligomers in the first class have reasonable water solubility and produce printed films with good properties, e.g. in terms of hardness and water resistance, but they have relatively high viscosities. Oligomers in the second class have higher water solubility and lower viscosity, but produce softer, more water sensitive films. By using a mixture of the two classes of oligomers, a good overall balance of properties can be achieved.
  • the alkoxylated trimethylolpropane acrylate monomer includes acrylates, methacrylates, and also multifunctional (meth)acrylates including di(meth)acrylates, tri(meth)acrylates etc.
  • the number of functionalities affects the properties of the resulting cured films, with higher functionality materials producing films with higher shrinkage, higher water/chemical resistance and better durability.
  • Higher functionality also provides fast cure response: materials with 1 or 2 functional groups usually cure/polymerise slowly and require a greater ratio of initiator and longer exposure to curing conditions.
  • the trimethylolpropane acrylate monomer may be alkoxylated etc. with ethoxylated monomers generally being preferred as they have good water solubility.
  • the extent of alkoxylation affects the water solubility of the monomer, and also the water sensitivity of the resulting printed material, with higher levels of alkoxylation producing more water soluble monomers and more water sensitive prints.
  • This material has a fast cure response and low skin irritancy and produces printed films with good properties including good water solvent resistance and lack of brittleness, i.e. good ductility.
  • Suitable commercially-available materials include the following UV-initiated free-radically curable materials available from Sartomer: SR 351TM (EO TMPTA), SR 454TM (EO 3 TMPTA), SR 492TM (TMPPOTA), SR 499TM (E06 TMPTA), SR 502TM (EO9 TMPTA), SR 9035TM (EO15 TMPTA), and the ethoxylated triacrylates from Rahn AG: MIRAMER 170TM, MIRAMER M3130TM. MIRAMER M3160TM and MIRAMER M3190TM.
  • the polyalkene glycol acrylate monomer includes acrylates, diacrylates, methacrylates and also multifunctional (meth)acrylates, including di(meth)acrylates, tri(meth)acrylates etc. Diacrylates are currently preferred. Compared with diacrylates, methacrylates and dimethacrylates have lower viscosities (which is advantageous), but slower cure responses (which is disadvantageous).
  • the polyalkene may be propylene, dipropylene etc., with dipropylene glycols being favoured.
  • the currently preferred material is dipropylene glycol diacrylate (DPGDA). DPGDA has the advantages of low viscosity, low volatility and fast cure speed, flexibility, adhesion, hardness and abrasion resistance.
  • Suitable commercially available materials include the following UV-initiated free-radically curable materials available from Sartomer: SR 508TM (DPGDA), SR 306TM (TPGDA), SR 238 (HDDA), SR 231TM (DEGDMA), SR 272TM (TEGDA), SR 205TM (TEGDMA), SR 268TM (TetEGDA), and SR 9003TM (PONPGDA), and the UV-initiated free-radically curable materials available from Cytec Industries including, but are not limited to: EBECRYL 114TM, EBECRYL 145TM and EBECRYL 152TM etc.
  • the composition includes one or more curable N-vinyl5monomer materials. These generally have low viscosities, and so act to reduce the viscosity of the compositions.
  • the N-vinyl monomers also act as curable humectants, helping jetting stability and printing reliability and preventing drying on the nozzles. They cure in with the epoxy and oxetane monomers, increasing film thickness. Because they cure in they do not have to be removed from the print before or after curing. It is preferred to use N-vinyl acetamide (N-VAM), N-vinyl pyrrolidone (NVP) or N-methyl-N-vinyl acetamide.
  • N-acryloyl morpholine (N-AM) (which is also curable) is a useful material.
  • N-AM N-acryloyl morpholine
  • the combination of N-vinyl acetamide and N-acryloyl morpholine has been found to give good results.
  • the N-vinyl monomer materials may also function as co-solvent.
  • the N-vinyl monomers are also surprisingly found to be useful in preventing or reducing kogation, and so function as anti kogation agents. These monomer materials may be used in an amount of up to about 35 % by weight of the total weight of the composition, but is typically used at levels of 30 % or less.
  • Viscosity values for various cationically- and free-radically curable materials are given below: Chemical Name Commercial Name Functionality Viscosity (mPas)@ 25°C Triethylene glycol divinyl ether TEGDVE 2 2.6 4-Hydroxybutyl vinyl ether HBVE 2 5.4 1,4 Butanediol divinyl ether BDVE 2 4.3 Trimethyloylpropane oxetane OXT-101 (TMPO) 1 22 3-Ethyl-3-(2-ethylhexylo xymethyl)oxetane OXT-212 2 5 Bis(3-ethyl-3-oxetanylmethyl)ether OXT-221 2 12.8 3,4-Epoxycyclo hexylmethyl-3,4-epoxy cyclohexane carboxylate ERL-4421, UVR-6105 2 220-250 Limonene monoxide LMO 1 10 Limonene dioxide LDO 2 10 N-methyl
  • NM-NVAM N-methyl-N-vinyl acetamide
  • Co-solvent may be desirably included in the compositions.
  • the co-solvent functions as a solvent for the curable materials and ideally has good compatibility with water and has low viscosity.
  • the co-solvent is typically selected from water-soluble organic solvents including alcohols, lactones, thiols, glycols, ethers etc.
  • Glycol ethers function well as co-solvents, as they have good water compatibility, low viscosities and, high boiling points. Further, glycol ethers function as humectants, preventing drying in print head nozzles. Ethylene glycol monobutyl ether (EGMBE) is particularly preferred.
  • Suitable co-solvents include, but are not limited to the following: isopropyl alcohol (IPA) (which gives good jetting), n-methyl pyrrolidone (NMP), methoxy propyl acetate (MPA) (which has a low viscosity), diacetone alcohol (DAA), methoxy propanol (MeOPr), methyl alcohol, ethyl alcohol, methyl lactate, ethyl lactate, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, 1-methyl-2-imidazolidinone, 1, 4-butanediol, dimethyl sulfoxide (DMSO), lactones, particularly ⁇ -butyrolactone, 2-propiolactone etc., glycol ethers, particularly propylene glycol n-butyl ether, dipropylene glycol, tripropylene glycol, 2-methyl-1, 3-propanediol, propylene glycol methyl ether, propylene glycol
  • curable monomers may also function as co-solvents, e.g. N-vinyl monomer materials such as N-acryloyl morpholine, N-methyl-N-vinyl acetamide and N-vinyl imidazole etc.
  • N-vinyl monomer materials such as N-acryloyl morpholine, N-methyl-N-vinyl acetamide and N-vinyl imidazole etc.
  • the presence of such materials, acting e.g. as supporting free-radically curable monomers renders additional co-solvent unnecessary.
  • the co-solvent is typically present in an amount in the range of up to 40 % by weight based on the total weight of the composition.
  • the composition optionally includes surfactant in small amount (say up to 1% by weight) to improve wetting.
  • Suitable surfactants can be selected having regard to the substrate on which the composition is to be printed.
  • Suitable surfactants include the following: Commercial name Chemical name Supplier BYK 333 Polyether modified poly-dimethylsiloxane BYK Chemie GmbH BYK 381 Ionic solution of polyacrylic copolymer BYK Chemie GmbH BYK 320 Polyether modified polymethylalkylsiloxane BYK Chemie GmbH BYK 307 Polyether modified dimethylsiloxane copolymer BYK Chemie GmbH BYK 302 Polyether modified dimethylsiloxane copolymer BYK Chemie GmbH FC 4430 Fluorosurfactant 3M FC 4432 Fluorosurfactant 3M Dynol 604 Non-ionic acetylenic glycol-based surfactant Air Products Surfadone LP 100 N-alkyl pyrrolidone ISP Surfy
  • Polyether modified polydimethylsiloxane surfactants e.g. BYK 333 in an amount from 0.2 to 0.8 % by weight, are currently favoured.
  • Suitable cationic photoinitiators for use in the present invention include, but are not limited to, onium salts selected from iodonium, sulfonium, phosphonium, arsonium, azonium, bromonium, or selenonium salts, and the like, and mixtures thereof.
  • Particularly preferred cationic photoinitiators are the diaryliodonium salts of sulphonic and boronic acids and their derivatives, and the triaryl sulfonium salts of sulphonic and boronic acids and their derivatives.
  • Examples of such materials include, but are not limited to, Cyracure UVI-6976, UVI-6990, UVI-6992 (Dow Chemicals), Irgacure 250, 261 and CGI 552, IGM-C440 (Ciba Specialty Chemicals), RP-2047 and UV9380c (Rhodia Co.), Esacure 1064, 1187 (Lamberti S.p.A) etc. (Cyracure and Irgacure and Esacure are Trade Marks).
  • compositions of the present invention desirably comprise from 1 to 20 % by weight of the cationic photoinitiator, preferably from 2 to 1.5 % by weight, and most preferably from 3 to 8 % by weight.
  • hybrid compositions according to the invention may additionally comprise a free-radical photoinitiator and a thermal initiator, photoinitiator etc.
  • Suitable free-radical initiators are well known to those skilled in the art, as are suitable levels of use (typically from 0.1 to 10 % by weight).
  • free radical initiators include, but are not limited to: organic peroxides, azo compounds, quinones, benzophenones, nitroso compounds, acryl halides, hydrozones, mercapto compounds, pyrylium compounds, triacrylimidazoles, bisimidazoles, chloroalkytriazines, benzoin ethers, benzil ketals, thioxanthones, and acetophenone derivatives, and mixtures thereof.
  • benzil methyl o-benzoate, benzoin, benzoin ethyl ether, benzoin isoproyl ether, benzoin isobutyl ether, benzophenone/tertiary amine, acetophenones such as 2.2-diethoxyacetophenone, benzyl methyl ketal, 1-hydroxycyclohexylhenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-dihenylphosphine oxide, 2-methyl-1-4(methylthio), phenyl-2-morpholino-1-propanone, bis(2.6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)
  • Suitable examples include, but are not limited to: Irgacure 2959, 184, 651, 750, 500, 127, 1800, 819, Darocur TPO, 1173 etc. (Ciba Specialty Chemicals) and Esacure KT046, KIP150, 75LT, KIP IT, KIP 100F, KIP EM, DP 250, KT37, EDB, H- Nu 470, H-Nu 470X, (Lamberti S.p.A) etc.
  • coinitiators may be used to cure the surface or the bulk of the printed fluid.
  • suitable coinitiators include, but are not limited to, N-371TM reactive amine coinitiator CN-386TM reactive amine coinitiator, CN-372TM reactive amine coinitiator, CN-384TM reactive amine coinitiator, CN-383TM reactive amine coinitiator, and CN-373TM reactive amine coinitiator, all from Sartomer.
  • oligomers may be added to the composition. Oligomers may be used to adjust various physical properties of the cured printed film, including chemical resistance, flexibility, weatherability, and shrinkage. Suitable oligomers that may be added to the radiation-curable thermal inkjet ink according to the present disclosure include, but are not limited to: polyesters and acrylics. Suitable amounts include, but are not limited to, amounts in a range of from 0.1 to 3 % by weight. CN-2302TM from Sartomer is currently preferred.
  • compositions of the invention may be used as is, e.g. to print a clear coating or layer or film on a substrate.
  • the compositions may be used as a vehicle e.g. for carrying a dye in solution or a dispersed pigment in known manner for printing of text or images.
  • the term colorant as used herein may refer to just a colorant, or it may refer to a colorant in combination with, for example, a dispersant of some kind.
  • the colorants used herein are dyes or pigments, more preferably pigments.
  • the colorant may be any colour, but preferably the colorant is cyan, magenta, yellow or black.
  • the colouring agent generally comprises a colorant which may be self-dispersed, polymer-dispersed or surfactant-dispersed.
  • a colorant which may be self-dispersed, polymer-dispersed or surfactant-dispersed.
  • self-dispersed pigment refers to pigments that have been chemically modified with a charge or a polymeric group, wherein the chemical modification aids the pigment in becoming and/or substantially remaining dispersed in a liquid vehicle.
  • the charging moiety is covalently-linked to the pigment.
  • Surfactant-dispersed pigment refers to pigments that utilize a surfactant dispersant to aid the pigment in becoming and/or substantially remaining dispersed in a liquid vehicle.
  • the colorant maybe chosen from a wide range of conventional colorants (pigments or dyes), preferably pigments.
  • the pigment is a white pigment, a black pigment, a blue pigment, a brown pigment, a cyan pigment, a green pigment, a violet pigment, a magenta pigment, a red pigment, or a yellow pigment, or shades or combinations thereof.
  • Suitable classes of coloured pigments include, for example, anthraquinones, phthalocyanine blues, phthalocyanine greens, diazos, monoazos, pyranthrones, perylenes, heterocyclic yellows, quinacridones, diketopyrolopyroles, and (thio)indigoids.
  • Such pigments are commercially available in either powder or press cake form from a number of sources including, BASF Corporation, Engelhard Corporation and Sun Chemical Corporation. Examples of other suitable coloured pigments are described in the Colour Index, 3rd edition (The Society of Dyers and Colourists, 1982 ).
  • the pigment particle size is as small as possible to enable a stable dispersion of the particles in the liquid vehicle and to prevent clogging of the ink channels or nozzle when the ink is used in an inkjet printer.
  • Preferred particle average diameters are generally from about 0.001 to about 0.3 micron, although the particle size can be outside this range in specific embodiments.
  • at least 70% of the pigment particles should have an average particle diameter of less than about 150 nm for carbon blacks and less than about 150 nm for colour pigments.
  • any suitable commercially available dye may be used to impart the desired colour characteristics to the inkjet ink.
  • Suitable anionic and cationic dyes are well known for use in inkjet inks, and include, but are not limited to the examples listed herein. Most inkjet ink dyes are anionic; however, cationic dyes may also be used.
  • Anionic dyes are those in which a negative charge is localized on one atom or spread over the entire molecule.
  • Cationic dyes are those in which a positive charge is localized on one atom or spread over the entire molecule.
  • the dye is present in the inkjet ink composition in any effective amount to provide a desired colour.
  • the dye is present in an amount of from about 1 to 5 % by weight of the ink composition, and preferably from about 1 to 4 % by weight (wherein the amount refers to an amount of dye molecules present in the ink), although the amount can be outside this range.
  • a mixture of dyes in the proportions desired to obtain a specific shade may also be employed.
  • the pigment may be present in the inkjet ink composition in any effective amount.
  • the pigment is present in an amount of from about 1 % to 5 % by weight of the ink composition and preferably from about 1 % to 3 % by weight, although the amount can be outside of this range. Where both dyes and pigments are incorporated into the inkjet ink composition, the weight percentage of the combined colorant may be adjusted accordingly.
  • additives such as pH adjusting agents, rust preventives, fungicides, antioxidants, evaporation accelerators, chelating agents, and water-soluble polymers other than the above described components, may be added into inks used in the present invention.
  • the ink of the present invention is preferably cured by UV irradiation and is suitable for application by thermal inkjet printing. Accordingly, the present invention also provides a method of inkjet printing comprising printing the abovementioned inkjet ink compositions onto a substrate, preferably a flexible non-porous substrate, and irradiating the ink.
  • the clear inkjet inks of the present invention can be prepared by any process suitable for formulating aqueous- or solvent-based curable materials.
  • Cationically-curable and hybrid inks are prepared by mixing the radiation-curable components: oxetane functional monomer(s), epoxy resin functional monomer(s), allyl and/or vinyl ether monomer(s), and photo-cationic initiator(s), and optional free-radical photoinitiator(s), in a high shear mixing apparatus, such as a commercially-available Dispermat SL-12-C1 bead mill [VMA Getzmann GmbH] (Dispermat is a Trade Mark) operating in recirculating mode at a rate of 4000 rpm for 10 minutes at a temperature of 25°C.
  • a high shear mixing apparatus such as a commercially-available Dispermat SL-12-C1 bead mill [VMA Getzmann GmbH] (Dispermat is a Trade Mark) operating in recirculating mode at a rate of 4
  • the milling media used was 0.1-0.7 ⁇ m ceramic beads.
  • the composition includes Irgacure 2959, the solid photoinitiator is first dissolved in sufficient quantity of the radiation-curable materials, and then high-shear mixed with the remaining components for 10 minutes.
  • the resulting clear inks were finally filtered (Whatman GF/B glass microfibre filter, 1 ⁇ m) to give a cationically-curable or hybrid ink suitable for thermal inkjet printing.
  • Viscosity measurements were performed using a Brookfield DV-II+ viscometer operating with a rotational speed of 60 rpm at a temperature of 25°C. Briefly, 17.5 ml of ink was transferred to the chamber, to which a suitable spindle was then lowered into the chamber and left until the temperature stabilized. Measurements were taken every 30, 60, 120 and 300 seconds, until a reproducible viscosity reading could be obtained. [Units: 1 mPa ⁇ s ⁇ 1 cP]
  • compositions were printed onto a range of different substrates at 600 x 600 dpi from a Wolke (Wolke is a Trade Mark) printer or from one of the following Hewlett Packard desktop printers HP 6127 and HP 850 using an HP45A cartridge (with capacity 43 ml ink) and then cured by exposure to UV from a 500 W Fusion Light Hammer 6 system equipped with an 'H' bulb, being conveyed below the UV system at a line speed of 30 m/min. (Fusion Light Hammer 6 is a Trade Mark).
  • the clear inks formulated according to the components in Tables 1 and 2 are in the form of a single-phase radiation-curable composition.
  • the formulated inks can also carry a dispersed pigment or dye.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Claims (13)

  1. Composition durcissable monophasée ayant une viscosité de 1 à 10 mPas à 25 °C telle que mesurée selon la description pour utilisation dans l'impression par jet d'encre thermique, comprenant au moins un matériau durcissable par voie cationique, au moins un photoinitiateur cationique et de l'eau, le matériau durcissable par voie cationique comprenant un monomère fonctionnel d'oxétane, et dans laquelle :
    a) soit le matériau durcissable par voie cationique comprend du monoxyde de limonène ou du dioxyde de limonène,
    b) soit la composition comporte au moins un matériau durcissable par voie radicalaire et comporte un ou plusieurs matériaux monomères N-vinyliques durcissables.
  2. Composition selon la revendication 1, qui comprend de 2 à 50 % en poids d'eau.
  3. Composition selon la revendication 2, qui comprend de 5 à 40 % en poids d'eau.
  4. Composition selon la revendication 3, qui comprend de 10 à 30 % en poids d'eau.
  5. Composition selon l'une quelconque des revendications précédentes, qui a une viscosité de 2 à 10 mPas à 25 °C.
  6. Composition selon la revendication 5, qui a une viscosité de 5 à 10 mPas à 25 °C.
  7. Composition selon l'une quelconque des revendications précédentes, qui comprend également un photoinitiateur radicalaire et au moins un matériau durcissable par voie radicalaire.
  8. Composition selon l'une quelconque des revendications précédentes, qui comprend un éther vinylique.
  9. Composition selon l'une quelconque des revendications précédentes, comprenant au moins un monomère d'acrylate.
  10. Composition selon l'une quelconque des revendications précédentes, qui comprend un pigment et/ou un colorant.
  11. Procédé d'impression par jet d'encre d'une composition selon l'une quelconque des revendications précédentes sur un substrat et d'irradiation de la composition une fois imprimée sur le substrat.
  12. Procédé selon la revendication 11, qui est réalisé par impression par jet d'encre thermique.
  13. Procédé selon la revendication 11 ou la revendication 12, dans lequel le substrat est non poreux.
EP07824530.5A 2006-11-09 2007-11-09 Impression par jet d'encre Expired - Fee Related EP2079774B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0622284.8A GB0622284D0 (en) 2006-11-09 2006-11-09 Inkjet printing
PCT/GB2007/004301 WO2008056172A1 (fr) 2006-11-09 2007-11-09 Impression par jet d'encre

Publications (2)

Publication Number Publication Date
EP2079774A1 EP2079774A1 (fr) 2009-07-22
EP2079774B1 true EP2079774B1 (fr) 2017-03-29

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EP07824530.5A Expired - Fee Related EP2079774B1 (fr) 2006-11-09 2007-11-09 Impression par jet d'encre

Country Status (6)

Country Link
US (1) US8476332B2 (fr)
EP (1) EP2079774B1 (fr)
JP (1) JP5685375B2 (fr)
CN (1) CN101595150B (fr)
GB (1) GB0622284D0 (fr)
WO (1) WO2008056172A1 (fr)

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JP5097395B2 (ja) * 2006-12-28 2012-12-12 株式会社リコー 記録用インク、インクメディアセット、インクカートリッジ、インクジェット記録方法、インクジェット記録装置、及びインク記録物
JP2008195882A (ja) * 2007-02-15 2008-08-28 Fujifilm Corp インクジェット記録用インク組成物、及び、インクジェット記録方法
JP5803582B2 (ja) 2011-05-12 2015-11-04 株式会社リコー 光重合性インクジェットインク、インクカートリッジ、プリンタ
US9393826B2 (en) 2011-10-24 2016-07-19 Hewlett-Packard Development Company, L.P. Inkjet recording medium, and method of using the same
JP6268953B2 (ja) 2012-11-19 2018-01-31 株式会社リコー 重合性インク組成物、インクカートリッジ、及びインクジェットプリンタ
US8926084B2 (en) 2012-11-22 2015-01-06 Ricoh Company, Ltd. Polymerizable ink composition, ink cartridge containing the same, and inkjet printer
EP2821240B1 (fr) * 2013-07-02 2016-06-01 Hewlett-Packard Industrial Printing Ltd. Procédés d'impression
US10604667B2 (en) 2014-06-26 2020-03-31 Cryovac, Llc Ink composition including polyurethane
CN106536644B (zh) * 2014-09-26 2019-10-18 株式会社Lg化学 可紫外光固化的油墨组合物、使用该组合物制造显示基板边框图案的方法及制造的边框图案
KR101813338B1 (ko) * 2014-12-11 2017-12-28 주식회사 엘지화학 베젤용 감광성 유색 잉크 조성물, 이를 이용하여 형성된 베젤 패턴 및 이를 포함하는 디스플레이 기판
US10604659B2 (en) 2015-06-08 2020-03-31 Dsm Ip Assets B.V. Liquid, hybrid UV/VIS radiation curable resin compositions for additive fabrication
US9873809B2 (en) * 2015-07-07 2018-01-23 Ricoh Company, Ltd. Ink, image forming method, image forming apparatus, and recorded matter
US9868869B2 (en) 2015-10-01 2018-01-16 R.R. Donnelley & Sons Company Ink composition for use on non-absorbent surfaces
KR102663364B1 (ko) 2015-10-01 2024-05-08 스트래터시스,인코포레이티드 적층식 제조용 액체 하이브리드 uv/가시광 복사선-경화성 수지 조성물
WO2018070654A1 (fr) * 2016-10-10 2018-04-19 주식회사 엘지화학 Composition d'encre à émission infrarouge destinée à l'impression à jet d'encre, procédé de formation d'un motif de lunette d'encadrement à l'aide de ladite composition, motif de lunette d'encadrement ainsi produit, et substrat d'affichage comprenant ladite composition
JP7215654B2 (ja) 2017-12-15 2023-01-31 コベストロ （ネザーランズ） ビー．ブイ． 粘性熱硬化性樹脂を高温噴射して、積層造形を介して固体物品を作製するための組成物及び方法
KR102333186B1 (ko) * 2018-08-17 2021-11-29 주식회사 엘지화학 필름 인쇄 가능한 자외선 경화형 잉크 조성물, 이를 이용한 베젤패턴의 제조방법, 이에 따라 제조한 베젤패턴 및 이를 포함하는 디스플레이 기판
DE102019123000A1 (de) * 2019-08-27 2021-03-04 Ferro Gmbh Drucksubstanz zur Beschichtung von Glasoberflächen
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Also Published As

Publication number Publication date
JP2010509426A (ja) 2010-03-25
US8476332B2 (en) 2013-07-02
EP2079774A1 (fr) 2009-07-22
CN101595150A (zh) 2009-12-02
JP5685375B2 (ja) 2015-03-18
WO2008056172A1 (fr) 2008-05-15
US20100068407A1 (en) 2010-03-18
CN101595150B (zh) 2013-04-17
GB0622284D0 (en) 2006-12-20

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